Process for the prodction of cosmetic creams and thickening agents therefor



PROCESS FOR THE PRGDUCTION OF COSMETIC CREAMS THICKENING AGENTS THERE- FDR Fritz Artur Vorsatz, 15 Eisenlohrstrasse, Karlsruhe, Germany No Drawing. Filed May 7, 1957, Ser. No. 651,479-

Claims priority, application Germany Jan. 3, 1953 3 Claims. (CL 167-87) This invention relates to a process of preparing clear,

transparent and easily removable aqueous jellies to serve as vehicles for cosmetic agents such as those employed, for example for hair dyeing, tinting, bleaching, waving and other types of treatment.

According to the invention, the above process come prises combining into a salt-like compound the hydrophobic cation of a higher cation-active organic base selected from the group consisting of ammonium and sulfonium compounds with the hydrophobic aniona'of a higher anion-active organic acid and gradually adding water to said salt-like compounduntil a desired consistency or gel is obtained. This application is a continuation-in-part of my abandoned application, Ser. No. 327,442, filed December 22, 1952.

The present invention relates also tomeans for-the treatment of hair, and more particularly to means for the dyeing and permanent waving of hair. It is preferable to employ the above said means in' the form of creams and the like, because it is advantageous to be able to localize the action of the reagents and to avoid an action on the skin of the person being treated. In the dyeing of hair, there are normally employed supports such as, e.g., fatty alcohols, stearates of glycol methyl :cellu- 40 or glycerol, polyox-yethylene derivatives, lose, carboxymethyl cellulose and. the like. 1

These cream bases, have a number 0t disadvantages such as, e.g., the tenacity with which they adhere: to the hair, whereby the rinsing is made a complicated operation, and the opacity of the creams.

In the permanent waving of hair, there isthe additional difiiculty that the winding up of the hair on curlers is made practically impossible if the treating product. must contain too much of the base to forma cream,,because the hair is then made. too slippery for being handled, Usually the means for permanent waving are therefore merely thickened or emulsion-like solutions,' -but-,not

creams.

It is an important object of the present invention to provide means to overcome the described difiiculties.

It is another object of the present invention to provide methods and means allowing the preparation of hairdyeing creams which are transparent, easy to apply and easy to remove from the hair.

It is a further object of the invention to prow'de methods and means for preparing a permanent. waving cream not subject to the aforementioned drawbacks.

It is a further object of the invention to provide means for the described purpose, which are inexpensive to manufacture and at the same time exert a useful influence on thehair being treated.

The invention accordingly consists of the compositions being determined by the appended claims.

I have found that the described deficiencies of known 70 products can be overcome if the aforesaid creams are prepared from new thickening bases which until now have 7 2' a 4 not been proposed. for hair-treating products. These new bases are salt-like compositions of high molecular organic bases and high molecular organic acids in substantially equi-molecular amounts.

.These organic high molecular bases derive from a basicfcentral atom, such as nitrogen, sulfur etc.; in other words they belong to the class of so-called onium-compounds. 'They contain at least one organic radical of 8 or more carbon. atoms and one -nitrogen atom or the like, with a basic reaction, andmaycontain other radicals of lower molecular weight.

r These products are often; named higher cation-active products because. oftheir ability to give foaming. solutions at, acid pI-Lvalue's, the: cation being the part of the molecule which carries the hydrophobic radical.

The organic high. molecular acids mentioned above contain atleast one organic radical of 8 ormore carbon atoms and at least one group with acid reaction as, for instance the. sulfonic acid radical, the carboxyl' radical, the radical of phosphoric-acid, etc. These products are often called higher anion-active products because in this case the anion is the part of the molecule which bears thehydmphobic greu The reaction products of these two components may be prepared by melting together the free base and the-free acid or, they may-be prepared by. douhlereaction-of their salts with low molecular basesandacids and contingently eliminating the byproducts.,; h i

They areavax-like substances that can be used as sup,- ports for cosmetic creams with. the, following advantages: (,1.-) They yield transparent, creams and thereby allow complete observation and. control of the action on the substrate as for instance the human hair.

2) fllhey allow the making-of such creams or gels with only a new percent of. the thickening base which makes. the productsvery inexpensive.

a (3) -If higherpercentagesare employed, the creams can. be diluted .withwater or aqueous solutions (e.g. H 05) withoutany lossofviscosity. 1 (4) They allow thepreparationgof 'cold-wave-cre'ams which in view of the low percentage of base are not slippery.

r I (5 On the other hand: anyother high molecular anion or cation than that of the base liquefies the cream almost instantaneously which: makes it possible to rinse the treating creamfvery easily ofi? the hair.

6) If the t-h'cke ing bases are dissolved together with the treatingcomposition in. organic hy'dro'philic solvents such as ethyl alcoh l, isopropyl alcohol, butanol, glycols, glycol monoalkyl ethersste -it is possible to prepare thin liquids which thicken instantaneously to a cream if there is. added water or an: aqueous solution.

I As already'known,cation active substances consist of high. molecular weight organic compounds containing one or more basic groupings derived from phosphorus, sulphur, oxygen or more particularly quaternary or nonquaternarynitrogen. Among. the better-known of these compounds. there may be mentioned the Sapamines of Ciba Ltd, the Soromines" of the B.A.S.F. and the Velan of I.C.I. Ltd. Compounds of this class are known. as invert soaps? and they are applied in the form of salts derived-from acids of; low molecular weight'such as methyl. sulphuric acid, acetic acid and hydrochloric acid in order to increase their solubility and to bring into eifect their cationsactive properties.

More particularly, some of the above Sapamines" are: chlorhyd-rate of oleyl-aminodiethyl amine, chlorhydratc ofv voleyl-benzylaminoethylenediethylamine, methylsulfate of monostearyl ethylene diaminetriethylammonium and methylsulfateof diethylaminoethyloleylamide asymmetric. fSome ofl1' the .,.Sor0mines are: stearic ester of'dibutylaminoethanol, monostearic ester of triethanolpatent d June 14, 1960 in the use of the compositions for the printing of fabrics,

am'ine' and hydroxyethylstearyl'amide condensed with 2 portions of the compounds. It'wi1l;be' i nderstood, how-. ever,that-other methods ofpreparatiQn may employed,

such as a redistribution reactionfin aqueous 'orfnon I aqueous solution or according :to. another? embodiment,

the quaternisation of the cation actiyegroupiimaybeef fectcd after the formation; of: a salt withthej Tani compound."

The new productsthus, obtainedpossess surprisingprop t a ir atiq mi ha s. m ch. as the waxes stand in relation to the'fat'sfi .The' compounds are a dye, or a cold permanent wave solution, causes an instantaneous thickening to the consistency 'of a cream.

The quantity of thickening liquid necessary is very low V with aqueous-solutions as, for example, a liquid" hair dye ea ivc I more soluble than their structure would IQSdQiIQJQjSQIF I pose. f'They have some" solubility in watenand in' particular, they yield, even inextremely, low concentrati ons', for example 0.5 to 5%, stable: creamsw hichcan readily be prepared by heating to'any suitablejtemperature up way. i

to 100 C. The creams thus obtained niaintaimin dis- I persion, other substances, suchfas; dyes, ammonium salts, thio'glycolates' and the like Theyihayeian attrace tive appearance and are of a'structure'comprisedbetyeen that of creams and that of jellies. I-n thin layersjthey for example, in the dyeing of ;A particularly valuable feature of the; creams produced according to the present invention appears frpni the folareperfectly transparent which'is an importiint feature, 2

n is known tha'tfthe strucui'eof creaniscanf beniodi fied very rapidly -byfadding"thereto"certain substances. in the present casefsuch modifying substances are those having active ions preferably other th'an thoselwhich are present in the thickening base itself. flfhus, for" example, a cream containing a stearoyl groupcan bef'lijquefied very rapidly 'by the addition as a fatty -ilcoliolsulphate;' As a "result one can 'pre'pare' c'reams for the ffdycing of hair which present all the advantages of the process of dyeing hair with the aid of cream,'silchasiiiiplicityflof and fixation of the dye 'whefe desirediand which possess; moreover, a complete transpare'ncy' permits to watch I the progress of thedyeing." removed by washing with a small qusnrity qr shampoo, aseasily as a liquid hair dye can be remove'i and all rnechanical which is converted'into a cream by the addition of hydrogen peroxide. I All these thickened preparations present the favourable properties indicatedabove and, in particular, the property of being readily removed by washing.

Products produced according to the invention have valuablehair-treating properties; 'It is known that cation-actiye compounds give to the hair brilliance and strength-. Further, they have an antiseptic efiect. 7 It is also known that-the -fat ty"acids and other anion active compounds have useful cosmetic properties. By means offihe present invention it is possible .to combine the favourable; effects of the two, classes of substances and to makev them usable in applications wherev their use was hitherto not possible ,7 The following examples will serve to illustrate the ventionbut are not to beregarded aslimitingit in any ".11.,Exxmm1; a 1'; I. Thickener Thereis heated on'a water bath 284 parts by-weight of. pure stearic acid and there is then added slowly, while stirring, 667 parts of dihydroxydi ethylen'etriamine distearylan'iide untilv aclear productis obtained. On e0 1; ing this' yields a waxy product; Said dihydroxydiethylenej triamine distearylamide corresponds to the formula '"crn,i -,co-Nn-onr-onon,

- 'onnu oo-Na-cn onon EXAMPLE Z, x I a Cream forper manent waving I {J 6 parts of the thickener described in Example 1, 6.2 'partpf borax, 3 parts of 'so rbitoi and 60. parts of: :wati" areheatedtoa boil. The product becomes homogeneous and, after cooling to 30 C., the desired quantities'of -am operations a're'avoided. Cre"amscont'ainingthethicken- I vantageoulyin permanent r11 9 are-brim lar value for this- "-pur'poe sin' the trernely simple and has no' effect;onthe freshlyobtained I wave. 1 l I jfl If 7:

These same propertie'sfplay an equallyfimportantpart esters, 'sorbitoL' glycerine',}formamide-and" the like.

. n w. f e conventional cream isthus'aVoidedf;Thewashing 'is'jexe I .ing a'gents "ofthe present invention may also beused' ad'- -m onium"thioglycolate and 'ammonia'are added to'bring the'total'to 1 00 parts. T EXA MPLEE h of the thickener .described. in Example l; are, dissolvedunder heating in 33 parts of 'isopropyl alcohol.

Thereis then added 67 parts of a solution of hair dye prepared in'a known manner; One volume ofthissolution is mixed' with two volumes of hydrogen peroxide (425%H5Q,) and there is thus obtained a creamyprepy EXiMPLs 14 i a Thereis mixed together 30 parts of lauryl sulfate,- for example the triethanolamine lauryl sulfatefiiparts'of ,a

thickening agent according to Example land parts of water, Coloring matter and perfumeis added as required.

' On warming this mixture on a water bath, a homogeneous "The properties. described-above mak'e itpos'sible tofob;

tain "entirely: new preparations. f- 'Ihu s; forf example, a

concentrated solution (about 10 to 20%) in organic solvent, upon addition to an aqueous solution, for example viscous. solution is obtained, forming an excellent sh-am EXAMPLES A solution of parts of cetyl-trimethylammoniumbromide in water is mixed with asolution of '142 parts of stearic acid inwater (neutralizedv with sodium hydroxide) II The reaction product which precipitates. is 'sfelimited anddriedk i 1 r. x is: "Two parts ,by weight of -this product dissolved in 15 parts by volume of ethyl.alcohol;tozthis solution is added? parts by volume of abi-rnolar acetic acid solu- 59 Pe -F? .P ilms yets I re a es dyesto preparea hair rinse.

EXAMPLE 6 In the same manner as in the preceding examplethere'is' prepared a reaction product of equimolecula'r tities of'the above cited cation and ananion-active product of the formula C H O.CH .CH .OCH .CH SO Na. To precipitate the reaction product, it is preferable --to add salt, e.g. ammonium sulfate.

Three parts by weight of the anion-cation-product are dissolved in 5 parts by volume of ethyl alcohol and mixed with 22 parts of Water. It results a jelly-like cream which can be alkalized; tag. with ammonia, or acidified e.g. with acetic acid or lactic acid. It may be taken as a base for hair-creams or for alkaline hair-bleaching creams, the latter for instance by diluting the ethanolic solution aqueous hydrogen peroxide instead of water.

It is also possible to prepare a cream from the described base simply by heating the anion-cation product with water and adding the other ingredients after cooling;

EXAMPLE. 7

In the'same way as in the preceding example there can be prepared a base with similar'propertie's by reacting cetyltrimethylammoniumbromide with ammonium dodecylsulfate;

The wax-like reaction product: gives a beautiful cream in mixtures of. alcohol and water. It may be taken as a base for a number of cosmetic treating products, such as hair dyes, vanishing creams and the like.

EXAMPLE 8 30 parts by weight of dihydroxydiethelenetriaminedistearylamide and 12 parts of myristic acid are melted f together while stirring. On cooling, there results a soft wax-like product.

3 parts by weight of this product are heated with 52 parts of water and added 5 parts by volume: of a 25% ammonium hydroxide solution after cooling. A beauti- :ful jelly-like cream is obtained. It may be used as: a base for hair-dyeing-creams, hair-bleaching creams, per- .manent waving creams and the like.

EXAMPLE 9 Thickener In place of. the waxy product, described in Example 1, there can be employed the product prepared as follows:

305 parts of sodium oleate dissolved in two thousand parts of distilled water are treated with 855 parts of a 40% solution of lauryldimethylsulfonium methosulfate without shaking. The anion-cation complex (lauryldimethylsulfonium oleate) precipitates "in dispersed form which is difiicult to separate persion is saturated with sodium chloride and the complex extracted with amyl alcohol. The extract is distilled under reduced pressure leaving a residue of waxy consistency.

EXAMPLE An aqueous solution of a compound of the following formula by centrifuging. The disbromide and of a taurate of the formula:

EXAMPLE 1'1' Removal of a hair tre'ating product An interesting feature of the aqueous jellies prepared in accordance with the invention relies on their easy removal. by application of. anv excess. of any suitable ionic and water-soluble surface active agent in aqueous solution, for instancean anionic or a cationic shampoo. This advantage. is evidenced by the: following tests.

One volume. ofa ten percent isopropanolic solution of the thickening, agent described in Example 1 was mixed with three volumes of-water. The resulting product isa cream having a viscosity of l-240-centipoises at 20 C. as measured with a Hoppler viscometer. By adding to 100 cc. of said cream 0.4 g. of ammonium dodecylsul'fate dissolved in 2 cc. of water, the structure of the cream is altered and the viscosity drops to 0.3 centipoises, i.e. a

value hardly higher than that of plain water.

' EXAMPLE 12 EXAMPLE 13 E'quimolecular amounts of cetyltrimethylammonium bromide and of a sarconsinate of the general formula:

Re-C OP -N-GHs-C O O'Na wherein represents. a. saturated aliphatic chain of 1 1 to (such as the product known as 13 carbon atoms Medialam KA) are mixed together invaqueous solution. A stifi. jelly is obtained which be used directly as a thickenerfor alkaline-solutions of aihighv salt content,,such

as permanent hair-waving solutions.

For instance, 15 parts'of crystallinesodium sulfite are dissolved in parts of the above-mentioned jelly, which contains 5 percent by; weight or theanion-cation complex.

30' parts by volume: of a bi-m'olar ammonium hydroxide solution are then-added. A cream is obtainedwhich can be used for permanent hair waving.

In an analogous manner, ammonium thioglycollate can be used in lieu of. sodium sulfite without noticeably altering the initial. consistency.

' EXAMPLE 14 Equimolecular amounts of cetyltrimethylammonium wherein R represents a saturated aliphatic chain of 11 to 13 carbon atoms, are mixed together, in aqueous medium. Upon gentle warming, two layers separate. The supernatant layer is decanted. It contains the anion-cation complex and 71.5% water. Upon cooling, it sets to a firm jelly which can be further diluted with water or with organic hydrophilic solvents.

For instance, a transparent gel is obtained by diluting 7.5 parts of the decanted layer with 25 parts of glycerol, 5 parts of water and 3 parts of ammonia (d=0.910).

is 7 ExAMP Efm M V r 'By proceeding in aQmanner analogous to that described in U.S.-Patent 2,193,963 (Harris) filed onApril .17, 1937, beta-hydroxyethyl methyl sulfide is reacted; with methyl iodide, the-resulting product is cooled in an ice-bath and esterified with n-decanoyl chloride in the presence of pyridine to yield the compound:; .21

'i .cm 7. "onl tonoecoo onwcnt-i cin I Q A7025 molar solution of said compound is then reacted with an equalqu'antity ofa 0.2 molar-solutionot'the condensation product of 2.5 moles of ethylene oxide with 1 mole of sodium laurylsulfate (commercial g'rade'lgsuch as the condensation product sold under the trade name Montapol K'l? by the French companyqroduits Chimiciues de la Montague Noire and which has a.2 7% content in active substance and an average molecular weight of 405.

Theresulting, precipitated compound corresponds to al es i m at x x 3;;

wherein R represents an aliphatic chain of 12 to 14 car-- b'on atoms; The 1 precipitate is separated and-dissolved 7 in 1.5 parts 'of beta-ethoxyethanoll ,A' clear'solution is obtained which can be further diluted with water to yield more'ior less viscous jellies,

V 1 In the appended cl ims, the term a higher cationactive organic base" is used-tomean a cation-active' base having 'a' hydrophobic-aliphatic chain of at least eight 'c'arbon atomsandthe term -a' higher anion-activeorganic acid is used to mean an anion-activei acid having a hydrophobic aliphatic chain of at leasteight carbon atoms, it 7 being understood that one or both of said aliphatic chains can be interrupted by .heteroatoms.

What'is claimed: is':' 1 i r 1: A? processof preparing 'clear, transparent and easily removable aqueous jellies to serve as vehicles for cosmetic 7 agents, which consists essentially of combining into a salt like compound the hydrophobic cation of a higher cationactive organic base selected from thegroup consisting of ammonium andsulfonium} compounds with an equimolecular quantity of the hydrophobicanion ofa higher' anionactive organic acid and adding water to -said salt-like compound to obtaina gel. f 1

- 2. A process ot-preparing clear, transparent and, easily removable aqueous jellies to serve as vehicles for cosmetic r '8 agents, which consists essentially of combining into a salt-like compound the hydrophobic-cation of a higher cation-active organic base with ahydrophobic homogeneous chain of at least eight'carbon atoms selected from the; group-'gconsisting ;of ammonium and sulfonium co'mpoundswith an equimolecular quantity of the hydrophobic anion of'a higher anion-active organic acid with a hydro: phobic homogeneous chain of at least eight-carbon atoms and adding water to said salt-like compound to obtain a predetermined consistency. o 3. A"process of preparing clear, transparent and easily removable aqueous'jellies to serve as vehicles for cosmetic 'agents,.which-ccnsis ts essentially of combining into a Salt-like; compound the hydrophobic'cation of a higher cation-active organic; base selected from the group consisting of ammonium and sulfonium compounds with the hydrophobic anion of a higher anion-active organic acid selected from the group consisting of higher fatty acids, acid'sulfates of higher .fatty alcohols and higher fatty acid derivatives of taurine and sarcosine, and adding water to said salt-like compound to obtain a predetermined consistency. V

4. A process according to claim 1, wherein the salt-like compound is obtained from the direct combinationof the free base with the free'acidJ 3 5. A process according 'to' claim 2, wherein the saltli ke compound is obtained from the direct combination of theefree base with the free acid.

6..A process according to. claim 1, wherein the saltlike compound; is obtained from'a'reaction between a water soluble salt of the: base and a water soluble salt of the acid. 7

7. A process according to claim 2, wherein the saltlike compound is obtained from a reaction between a water soluble salt of'the base and a water soluble salt of the'acid. i e i 8. A methodof preparing cosmetic jellies which consists essentially of "dissolving into an organic hydrophilic solvent a cosmetic agent and a salt-like compound obtained from the combination of the hydrophobic cation ofia higher cation-active organic base selected from the group consisting of ammonium and sulfonium compounds with the hydrophobic anion ofa higher anion-active or"- ganic acid and adding water .tothe resulting solution to obtain a predeterminedconsistency.

References Qited in the tile of this patent r UNITED STATES PATENTS r Kritchevsky Aug. 10, 1957 2,166,127 Cahn a a1.: July 18, 939 I 2,208,594. Orelup; July 23, 1940 2,268,736 Buxton et a1. Jan. 6, 1942 "2,577,773 Lambert Dec. 11, 1951 '2,617,754 Neely '..'Nov. 11, 1952 I; .g FOREIGN PATENTS 5 278,403 Switzerland Jan. 16, 1952 v '1 OTHER REFERENCES 1 Schwartz and Perry: Surface Active Agents, vol. I

' Reinisch: J. S. Cos. Chemists, vol. 5, No. 3, November Harry: Modern Cosmeticology, 4th ed., vol. 1, Leonard Hill; Ltd London, 1955, p. 422. V

Gonon; La Parfumerie Moderne, vol. 40, No. 11',

December 1948, pp. 4 2-49. 

2. A PROCESS OF PREPARING CLEAR, TRANSPARENT AND EASILY REMOVABLE AQUEOUS JELLIES TO SERVE AS VEHICLES FOR COSMETIC AGENTS, WHICH CONSISTS ESSENTIALLY OF COMBINING INTO A SALT-LIKE COMPOUND THE HYDROPHOBIC CATION OF A HIGHER CATION-ACTIVE ORGANIC BASE WITH A HYDROPHOBIC HOMOGENEOUS CHAIN OF AT LEAST EIGHT CARBON ATOMS SELECTED FROM THE GROUP CONSISTING OF AMMONIUM AND SULFONIUM COMPOUNDS WITH AN EQUIMOLECULAR QUANTITY OF THE HYDROPHOBIC ANION OF A HIGHER ANION-ACTIVE ORGANIC ACID WITH A HYDROPHOBIC HOMOGENEOUS CHAIN OF AT LEAST EIGHT CARBON ATOMS AND ADDING WATER TO SAID SALT-LIKE COMPOUND TO OBTAIN A PREDETERMINED CONSISTENCY. 